Dyeing of human hair with cationic direct dyes



United States Patent 3,482,923 DYEING OF HUMAN HAIR WITH CATIONIC DIRECT DYES Karl-Josef Boosen, Dusseldorf, Holthausen, 'Peter Berth, Dusseldorf, Benrath, and Gunter Reese, Dusseldorf, Germany, assignors to Therachemie Chemisch Therapeutische Gesellschaft m.b.H., Dusseldorf, Germany No Drawing. Filed Aug. 25, 1965, Ser. No. 482,628 Claims priority, application Germany, Sept. 2, 1964, T 26,921 Int. Cl. A61k 7/12 US. Cl. 8-10.1 14 Claims ABSTRACT OF THE DISCLOSURE This invention relates to the improved dyeing of hair, particularly human hair,'with cationic direct dyestuffs. The dyeing is improved by ketones, esters, pyridine and derivatives thereof, as well as ethylene glycol carbonate, tetrahydrothiophene dioxide and thionaphthene.

The invention relates to boosters for cationic direct dyestuffs which facilitate the dyeing of hair, more particularly human hair, and to a process for their application.

For the dyeing of hair so-called oxidation dyes are employed on a large scale, such as aromatic diamines, aminopheuols or polyhydroxy compounds. However, direct dyes also have been used which have the advantage not to require the addition of oxidizers upon application. It is known from the textile industry that dyeing and the qualities of the coloring obtained thereby can frequently be improved by means of particularly high or low pH values, elevated temperatures or extension of the time of application. Upon dyeing of hair, and particularly living human hair, such methods evidently cannot be employed. Moreover, it often is necessary to apply entirely new dyes as agents for dyeing of humanhair, and this is especially true for direct dyes.

It also has been attempted to improve theusefulness especially of such dyes of limited solubility, by the addition of materials as butanol, benzyl alcohol or'addition duction of the latter or else shortly before its application to the hair. Concentrations and temperatures are the same as named above.

1 The advantages of this novel process are found in the factthat frequently the quantity of dyestuff to be applied can materially be reduced Without sacrificing the intensity ofthe dye. It also is feasible in many instances to increase the color intensity considerably with the process according to the invention when initially a rather weak coloration is present. a I

A further advantage is the increase in the resistance to abrasion and rubbing with simultaneous improvement of the dyeing process.

The single effects depend, to a certain extent, on the booster used and on the characteristics of the dyestuif itself, but it has been established that the improvements named have been attained in all instances. For practical application, the compounds named below are particularly interesting from a technological and economical point of view. They are special representatives of (a)(c) above,

but are not presented to be a limitation:

products of phenols -or alcohols on ethylene oxide. How

hair with solutions, dispersions or emulsions of compounds of the following series:

a) ketones having 5 to 10 carbon atoms; (b) esters of saturated aliphatic and aromatic carboxylic acids having 2 to 8 carbon atoms with alcohols having 1 to 8 carbon atoms;

(c) pyridine and its derivatives; i

(d) ethylene glycol carbonate, tetrahydrothiophene dioxide, thionaphthene.

Treatment of the hair can be carried out by rinsing it with a solution or emulsion containing one or more of the compounds named above, followed by dyeing with the direct dyes in the conventional manner. However, it is equally feasible to wash the hair first and to add the agents to the last rinse directly. The concentration of the agents ranges from 0.1 to 10 weight percent, preferably 1 to 5 percent. The temperatures are 15 to 40 C., preferably room temperature. a

If desired, this treatment furthermore can be combined with the actual dyeing by incorporating the compounds (a) cyclopentanone, cyclohexanone, 2-ethylcyclohexanone,

2-propylcyclohexanone, .acetophenone, p-methoxyacetophenone; (b) propylacetate, butylacetate, amylacetate, isoamylacetate, octylacetate, cyclohexylacetate, propylbutyrate,

ethylbenzoate, p-nitrobenzoic acid methyl ester, diethyloxalate, diethylmalonate, dimethyladipate, diethyl phthalate;

If desired, mixtures of these compounds can be used, especially mixtures of compounds of the same group. It goes without saying that the mutual chemical compatibility and that with other possibly present materials must be considered.

The pH value of the solutions containing these boosters can be adapted to a large measure to the prevailing requirements anddesires. Good results have been obtained with preparing solutions and/ or last rinses which were not alkaline, but'acid or neutral. 7

Suitable cationic direct dyestuffs are those commonly known 'forfthe' purpose at hand, especially those'based upon triphenylmethane, azines, oxazine and thiazine'i Particularly well known compounds are crystal violet, fuchsin, methylene blue or else compounds having Formulae 1 and 2: Y

percent. If, however, the effect of an increased color intensity is not desired, the commonly employed quantities can greatly be decreased, in some instances down to approximately of the usual amount, with the process according to the invention.

The hair dyes can be mixed with wetting agents, detergents and washing agents, especially with those which are nonionic. Aminooxides, fatty acid ethanolamides, addition products of ethylene oxide on fatty acids and fatty alcohols are especially suited.

Furthermore, thickeners can be added, such as methylcellulose, starch, higher fatty alcohols, Vaseline, panafiin oil and fatty acids; also perfumes, i.e., essential oils, or hair grooming agents such as pantotheuic acid and cholesterol.

These additives are incorporated in the commonly used quantities. As wetting agent or detergent amounts of 0.5-30 weight percent, as thickeners 0.1-25 weight percent, are preferred, calculated on the total composition. The concentration of the dyes, depending upon the purpose, amounts to up to weight percent, preferably however, 0.1 to 2 weight percent, calculated on the total composition.

The invention now will be further illustrated by the following Examples.

EXAMPLE 1 Naturally greyed human living hair was washed with a shampoo and rinsed repeatedly. The 'last rinse water contained 5 weight percent N-methylpicolinic acid thioamide. The hair then was treated with a dyeing cream containing as cation-active dye 0.1 weight percent fuchsin. The pH of the cream was 9.5, the time of application 30 minutes at room temperature. A good red-purple color was obtained whose intensity was considerably stronger than that of hair which had been treated in the same manner with the exception that the additive to the last rinse water had been omitted.

A considerable boost in the color intensity also occurred when the hair to be dyed, prior to dyeing, was rinsed with an aqueous solution of 3 weight percent methylpicolinic acid thioamide.

EXAMPLE 2 Grey hair was treated with an aqueous-ammoniacal 0.1 weight percent fuchsin solution of a pH of 9.5 at room temperature. A red coloration thereby was obtained.

A considerable stronger deep red color resulted when the same grey hair, prior to dyeing in the same manner, was treated for 5 minutes at room temperature with an aqueous-ammoniacal 5 weight percent suspension of N- methylpicolinic acid thioamide.

Practically the same result is obtained when the rinse with the above suspension is carried out with the suspension reacting neutral or at pH of 2.

EXAMPLE 3 A hair dye in cream form was prepared by heating weight parts cetyl-stearyl alcohol and 8 parts lauryldimethylaminooxide to 80 C. and emulsifying with 60 weight parts water of like temperature. After cooling, a solution of 1 weight part of a dyestuff having Formula 3 in parts water was added, the pH adjusted to 9 with aqueous ammonia, and the solution made up to 100 weight parts with water. The cream thus obtained dyed grey hair yellow within 30 minutes at room temperature.

When the cream as described above further contained 5 weight percent p-aminoacetophenone, the hair assumed a b illiant yellow color of much higher intensity.

4 EXAMPLE 4 A hair dyeing agent in gel form was prepared by dis solving 2 weight parts of a dyestutf having Formula 4 in a transparent paste consisting of 10 weight parts of equal amounts of cetyl and stearyl alcohol and 15 weight parts of the reaction product of lauryl alcohol with 10 mols ethylene oxide and 73 parts water. This gel paste dyed hair weakly yellow within 30 minutes at room temperature.

When in this dyeing agent simultaneously 3 weight parts pyridine-2-aldehyde were incorporated, a strong yellow color developed under the same conditions.

A strong yellow color also is obtained when the amount of dyestuff is decreased from 2 weight parts to 1 weight part and additionally 5 weight parts dimethyladipate are incorporated in the dyeing agent.

EXAMPLE 5 A dyeing agent as described in the preceding example was prepared except that as dyestuff 0.5 weight parts fuchsin were employed. Grey hair was treated with the agent for 25 minutes at body temperature and assumed ared color.

The color becomes brilliantly red-purple when the dyeing cream also contains 4 weight parts acetophenone.

EXAMPLE 6 Aqueous solutions were produced containing as cationic dyestulf 0.3 weight percent crystal violet and, as a further additive, one of the compounds listed, together with the appropriate quantities to be used, in Table 1. The solutions were adjusted to a pH of 9.5 with aqueous ammonia. Grey human hair was treated with these compounds for 20 minutes at room temperature, followed by shampooing and drying.

In all instances, the coloring was substantially improved over the light purple color obtained under otherwise equal operating conditions, but without the additives named in Table 1.

Corresponding results were obtained when, in lieu of the crystal violet, a dye was used as named and indexed in Table 2.

TABLE 1 Weight.

Gyclopentanone... Cyclohexanone 2-ethy1cyclohex anona 2-propylcyclohexanone a Acetophenone Drethyloxalatm Dimethyladipate Diethylphthalate. Pyridine-2-carbiuol Py1idine-2-thiocarbinol Pyridine-EI-caroinol Pyridiue-2-ethanol PyIidine-Z-aldehyde Pyridine-2aldoxirne Pyridine-2,6-dicarboxy c a 27 Nicotinic acid TABLE 1.- -Con tinued I I i V 7 Weight No. Material v i y r percent Isonico tinic acid thiomide 1 'Pyridine-2-carboxylic acid n-butyl- 1 posters Y Pyridyl-3-acry1ic acid 4 2-cyanopyr'idine; 3 -picol-ylamlne. 2 2-picolylmethylamme 2 P er-idine r 4 Piperazine hydrate. A 2,2-pyridil 2 Ethyleneglycol carbonate 2 Thionaphthene t. 2 Pyridine 4 TABLE 2 Color Index Dyestut'x' N 0.

Victoria Blue R 44 040 (CZHQHN- O =N(CH3)2] Cl- Astrazone Yellow 3G l. 48 055 NCCH=OHHN i C1- H 30 -0 CH3 Rhoda-mine B Extra 45 170 Q VN(C2H5)'1}Cl" C O O H Astrfadiamond' Green GX 42 040 /,N(C2H5 a H 2 a)2}HSO4 Rhodamine 4 GD l 45 160 C O O CzHa Dyes named in U.S. Patent 3,100,739.

What is claimed is:

1. A process for boosting the act ionof a cationic direct dye on human hair whichcomprises treating said hair prior to the application of said dye with a liquidselected from the group consisting of aqueous solutions and dispersions at temperatures of substantially 15 to 40 C., said liquids containing substantially 0.5 to -weight percent of compounds taken-from theclass-consisting of cyclopentanone, cyclohexanone, 2-ethyl cyclohexanone, 2-propyl cyclohexanone, acetophenone, p-methoxy acetophenone, and mixtures thereof.

2. A process according to claim 1 wherein said dye is taken from the class consisting of crystal violet, fuchsin, methylene blue,

and

Zi- H30 611 COOH H300 OCH 3. A process for boosting the action of a cationic direct dye on human hair which comprises treating said hair 'priorto the application of said dye with a liquid selected from the group consistingof aqueous solutions and dispersions at temperatures of substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 Weight percent of compounds taken from the class consisting of .pyridine-'2-carbin0l, pyridine 2 thiocarbinol, pyridine-3- prior to the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures of substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of compounds taken from the class consisting of ethylene glycol carbonate, tetrahydrothiophene dioxide, thionaphthene, and mixtures thereof.

5. A process for boosting the action of a cationic direct dye on human hair which comprises treating said hair prior to the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures of substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of cyclohexyl acetate.

6. A process for boosting the action of a cationic direct dye on human hair which comprises treating said hair prior to the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures of substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of p-nitro benzoic acid methyl ester.

7. A process for boosting the action of a cationic direct dye on human hair which comprises treating said hair prior to the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures of substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of diethyl phthalate.

8. A process for boosting the action of a cationic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures of substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of compounds taken from the class consisting of cyclopentanone, cyclohexanone, Z-ethyl cyclohexanone, 2-propy1 cyclohexanone, acetophenone, p-methoxy acetophenone, and mixtures thereof.

9. A process for boosting the action of a cationic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures of substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of compounds taken from the class consisting of pyridine 2 carbinol, pyridine-Z-thiocarbinol, pyridiue-S-carbinol, pyridine 2 ethanol, pyridine-Z-aldehyde, pyridine-Z-aldoxime, pyridine-2,6-dicarboxylic acid, nicotinic acid, isonicotinic acid thioamide, pyridine-Z-carboxylic acid-n-butylester, pyridyl-3-acrylic acid, Z-cyanopyridine, 2 picolylamine, 2 picolylmethylamine, piperidine, piperazine hydrate, 2,2'-pyridil, and mixtures thereof.

10. A process for boosting the action of a cationic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures of substantially 15 to 40 C., said liquids containing substantially 0.5 to 10 weight percent of compounds taken from the class consistingof ethylene glycol carbonate, tetrahydrothiophene dioxide, thionaphthene, and mixtures thereof.

11. A process for boosting the action of a cationic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures of substantially 15 to 40 C., said liquids containing substantially 05m weight percent of cyclohexyl acetate.

12. A process for boosting the action of a cationic direct dye on human hair which comprises treating said hair simultaneously with the application of said dye with a liquid selected from the group consisting of aqueous solutions and dispersions at temperatures of substantially to 40 C., said liquids containing substantially 0.5 to 10 weight percent of p-nitro benzoic acid methyl ester.

solutions and dispersions at temperatures of substantially 15 to 40 C., said liquids containing substantially 0.5 t 10 weight percent of diethyl phthalate.

14. A process according to claim 8 wherein said dye is taken from the class consisting of crystal violet, fuchsin, methylene blue,

S CHaU \0 (15) (OH) a 2 f/ CH and Hz 3)s N02 Cl(-) TABLE 2 Ft Dyestufi Ni:

Victoria Blue R 44 040 @Nwnm zHa)HN C v N(OH:)2} Cl" Astrazone Yellow 3G 48 055 N= CH=CH-HN w- 113C 01- H300 OCHa Rhodamine B Extra 45 170 uncalN- -o Glacial: l/

O O OH Astradiamond Green GX 42 040 /C 2H5)z 3 "'N(CHa)2} H304 Rhodamine 4 GD 45 Dyes named in U.S. Patent 3,100,739.

(References on following page) 9 10 Referen'ces Cited ALBERT T. MEYERS, Primary Examiner UNITED STATES PATENTS V. C. CLARKE, Assistant Examiner 2,069,215 2/1937 Chambers 8-85X 2,585,610 2/1952 Wittwer 8-10 5 US FOREIGN PATENTS 83, 85,9193

239,365 7/1962 Australia. 

